Printing composition and method of manufacture



Patented Nov. 8, 1938 UNITED STATES PATENT OFFICE 2,136,108 PRINTING COMPOSITION AND METHOD OF MANUFACTURE- No Drawing. Application April 21, 1936, Serial No. 75,576

11 Claims.

This invention relates to a fast-drying vehicle especially adapted for coatings and printing ink compositions and to the method of manufacturing and drying the composition. More specifically, the invention relates to coatings and a printing ink composition which, when applied to the surface receiving the fast-drying composition, dries in a hard, non-smearing and non-olfsetting film in a very few seconds of time.

Certain oils, and especially China-wood oil, possess very valuable drying properties, but due to the comparative slow-drying of the oils through oxidation and difiiculty in controlling the film,

. the oils have not been entirely satisfactory in the manufacture of printing inks, as commercially acceptable printing inks must necessarily dry into hard films with substantially no smearing and off-setting in a short period of time. In the present application, I disclosea composition and process of manufacturing, whereby China-wood oil and other oils,.when properly treated, yield a printing ink which dries in a few seconds of time, and the film will be hard with substantially no smearing or cit-setting.

It is, therefore, an object of my invention to produce a fast-drying vehicle adapted to be used in printing ink compositions which dries'relatively fast so that it can be used with presses when operating at a high rate of speed without onsetting. As has been generally recognized, operations are interrupted in printing to allow the printed material on one side of the printed sheet to dry before the sheet is printed on the opposite side, and, consequently, the speed of production of printed materials was somewhat restricted. Inks, hereinafter described as my invention, have dried into hard films with substantially no 01fsetting or smearing in approximately two seconds of time at elevated temperatures after its application to the surface under actual printing operation, and the drying is so rapid that it is possible to print both sides of v the pattern in a continuous operation. Thus, through the application of my printing inks to high speed presses, printing operations can be materially speeded up with the printed material being better'in quality than the printed material previously obtained.

A further object of my invention is to produce .a printing ink which when printed and the printed material is stacked in heaps or rolls, there will be no harmful evolution of heat. In the case of inks in which the drying of the ink occurs through oxidation, heat is evolved during the drying, and if the printed sheets are stacked in heaps or rolls, the stacks may ignite or scorch through spontaneous combustion. Printed material, which has been printed with the ink described as my invention, can be stacked or rolled immediately after being printed and neither smearing, ofi-setting nor any danger of spontaneous combustion is present.

A still further object of my invention is to produce a printing ink in which the viscosity may be regulated thereby giving a wide range of working properties. invention may be made in a range of viscosities extending from light to heavy bodies and the rapidity of drying will not be retarded. This wide flexibility of viscosity control gives the ink great advantages over inks heretofore used.

An additional, object of my invention is to prepare a fast-drying vehicle which may be used as a coating composition in any industrial activity wherever coatings. are necessary. Such applications include coatings used in the manufacture of linoleum and felt base materials, protective coatings for automobiles, furniture and other articles of manufacture. Throughout the description in my specification, I will describe the application of my fast-drying vehicle as applied to printing inks, but it is understood that the specific description shall not be construed as excluding the application of my fast-drying vehicles in places wherever coating compositions are used.

Several distinct advantages, such as the absence of oil-setting, and no smearing immediately after printing, and substantially no evolution of heat after the printed material is, stacked in heaps, have been discussed, but numerous other advantages of my ink will be apparent to those skilled in the art.

Heretofore, printing inks containing oils con: sisted primarily of heavy bodied oils which, on being applied to a surface, were dried through oxidation. In the case of drying through oxidation, drying first occurs at the surface of the film and the interior of the film necessarily dries much slower since the oxidized surface prevents easy access of oxygen to the interior of the film. These conditions thus cause the inks to smear easily and off-setting will occur if the printed materials are stacked in heaps. Through the application of my invention to printing operations, the drying of the ink film will dry substantially instantaneously and uniformly throughout its entire thickness through a chemical reaction, thereby eliminating the objections commonly present in printing inks now universally used.

In my co-pending application on printing inks Inks made in accordance with my and claimed a printing ink which dries very rapidly through a condensation reaction between oils having double bonds in conjugate arrangement and a condensing agent chosen from a specified group. In my present invention, a drying or semi-drying oil is also essential for the successful operation of my invention, but the treatment of the oil to reach the desired result is entirely different as will hereinafter be revealed.

Broadly speaking, my present invention comprises the method of drying chlorinated oil vehicles in which the drying reaction is caused by a chemical reaction between the oil vehicle and an activating agent. The reaction may occur at normal atmospheric temperatures, or it may occur at super-atmospheric or elevated temperatures. As a general rule, the reaction occurs at elevated temperatures.

In preparing my oil vehicles used in the present invention, drying oils, including China-wood, oiticica, linseed, perilla and fish oils are particularly suitable for the successful operation of my invention. In the field of semi-drying oils, I have found that oils such as scya bean oil, hempseed oil, rapeseed oil, poppyseed oil, safflower oil, etc., can be used with equal adaptation as the drying oils mentioned above. It is, therefore, understood in this particular invention that at any point in the specification or claims of this invention where the term oil is used, I intend to include only drying oils and semi-drying oils, or mixtures thereof, within the scope of my invention. If semi-drying oils are used, the rate of reactivity is retarded, but the reaction will occur in the same manner as in the case of drying oils. Mineral oils or non-drying oils are not included within the scope of the present invention.

The oil used in the preparation of the vehicle is treated with chlorine and the chlorine will attach itself to the unsaturated bonds present in the oil chain. The degree of chlorination of the oil is quite important in the production of my fast-drying ink, since the speed of the reaction depends upon the degree of chlorination. For example, in (ii-chlorinated china-wood oil, wherein two atoms of chlorine are attached to one unsaturation of the nine unsaturated bonds found in the glyceride structure of China-wood oil,the reactivity of the vehicle is much slower than in the case of tetra-chlorinated China-wood oil. In the case of tetra-chlorinated China-wood oil, four atoms of chlorine are attached to two unsaturations of the existing nine found in the glyceride structure. Furthermore, in the case of hexachlorinated China-wood oil, where six atoms of chlorine are attached to three unsaturations of the glyceride structure, the drying reactivity of the vehicle is much faster than in the case of dichlorinated and tetra-chlorinated oils. It is thus obvious that as the degree of chlorination of the oil vehicle is increased, the degree of reactivity is likewise increased.

Other halogens, such as bromine and iodine, may be used in place of chlorine, but the resulting halogenated oil product is relatively unstable, and the treated oil must, therefore, be used in a relatively short time after preparation. It is my belief that the brominated product is less satisfactory than the chlorinated product, because of the tendency of the bromine to convert the alphaeleastearin of the oil to the beta-glyceride. In the case of iodine, the oil is more unstable than in the case of bromine, since the presence of a small quantity of iodine (as low as .03% iodine) was a,1so,1os

No. 82,918 filed June '1, rose, 1 have described sufficient to produce a conversion in twenty-four hours. For all practical purposes of my invention, chlorine gives the best and most satisfactory results, but bromine and iodine may be used under the conditions enumerated above.

In preparing my oilvehicle, I have found that oxidized and polymerized oils may be used as well as the raw oils. Also, mixtures of raw oils, oxidized and polymerized oils have given excellent vehicles and are included within the scope of my invention.

The activating agent is a metallic paste compound in the oxide or hydroxide form, chosen from the group of the following metals: Zinc, iron, mercury, antimony, copper, tin, cobalt, nickel, chromium and magnesium or mixtures of the above metallic compounds. It is, therefore, understood that throughout the specifications and claims, where the term metallic substance is used, I include only the oxides and hydroxides of the metals enmuerated, viz., zinc, iron, mercury, antimony, copper, tin, cobalt, nickel, chromium, magnesium or mixtures of said metallic compounds. Zinc and iron appear to be the best activating agents in the above group, and are used as a general rule as the activating agents in drying the chlorinated oil vehicle described above. The metallic activating agent is generally prepared in a paste in which the metallic oxide or hydroxide particles are wetted by a film of water. The water acts in the nature of a protective means since the water film wetting the metallic oxide or hydroxide particle prevents the chemical reaction between the chlorinated oil and the activating agent from starting, until it is so desired. It is desirable that the inter-facial tension between the metallic activating agent and the water should preferably be less than the inter-facial tension between the activating agent and the oil, and the protective action of the water varies directly as the magnitude of the difference. Stated more specifically, the activating agent should be of such a nature that the activating agent will be wetted preferentially by the water rather than the oil. When it is desired to have the chemical reaction between the oil and the activating agent to occur, the mere application of heat will tend to drive off the water wetting the metallic com pound-particles and the reaction between the chlorinated oil and the metallic compound will occur.

In the event the ink is ture, the metallic oxide or hydroxide will react with the treated oil as soon as sufficient water has evaporated to break down the water film wetting the metallic compound molecules. However, as a general rule, I prefer the application of heat, since the reaction is more rapid under these circumstances.

The chemical reaction between 'the mixed chlorinated oil and the activating agent is an exothermic reaction, and it is only necessary to apply a comparatively low temperature to the mixed chlorinated oil and the activating agent in order to have the chemical reaction start. The heat given ofl by the reacting products is sufficient to cause the reaction to go to completion without any further application of heat. If, however, external heat is applied at high temperatures, the reaction will tend to go to completion in a much faster time.

Resins in the form of a varnish may be added to the chlorinated oil prior to the time the activating agent is added to the chlorinated oil. Through the medium of the resins, various physidried at room tempera- I to better advantage.

cal properties of the oil vehicle may be controlled The properties, such as better control of the viscosity of the vehicle, improvement in the stability of the liquid ink at room temperature, and toughness and pliability of the hardened ink film, result from the addition of the resin. The resins which may be used include rosin, ester gum, phenol-aldehyde resins,

etc. If resins are used, the higher melting point resins are preferred.

Having disclosed and described the method of preparing the treated oil and the activating agent, I will now disclose specific examples which embody the principles of my invention. The formulations described below are merely descriptive 'of several of the many formulations which may 'be eifected in printing inks and do not in any way cover the many various modifications of my invention:

Example Parts/100 Di-chlorinated oil (China-wood oil) 48 gallon cumar resin varnish 48 York whiting l. Zinc aluminum hydroxide paste 3 In the above example, the China-wood oil is tached to one of the nine double bond saturations in the glyceride structure. Forty-eight parts of a 30-gallon cumar resin varnish are then mixed with the chlorinated oil. The corner resin varnish is prepared, as follows:

, Per cent China-wood oil 70.2 Cumar resin 29.8

About one-half of the oil and the resin are mixed and heated to approximately 560 F. until the resin is dissolved. The remainder of the oil is' then added and the mixture is cooled.

The activating agent, viz., the zinc aluminum hydroxide paste, is made, as follows:

Grams Zinc chloride 40 Aluminum chloride 3 64 The ammonium hydroxide is added to the solution of the chlorides quite slowly while continuously stirring the mixture. The zinc and aluminum' will precipitate,both metals being in the hydroxide form. The solution is filtered and the zinc-aluminum hydroxide paste remains, which may then, if "necessary, be pressed to reduce the free water content of the precipitated paste. The presence of the aluminum is desirable in that it gives improved physical properties to the paste.

The zinc-aluminum hydroxide paste is then carefully mixed with the chlorinated oil and, at the same time, the whiting may be added. The whiting is unnecessary, but in some cases, it tends to stabilize the ink.

In preparing fast-dr "lg vehicles as described After the printing ink has been mixed as described above, it is ready for immediate use. The ink is placed in the conventional color carriages and printed in the conventional manner. Heat is generally applied immediately after printl ing the clorinated oil and the activating agent,

and the drying of the ink occurs in a very few seconds of time.

Another formulation is, as follows:

' Parts/100 Hexa-chlorinated China-wood oil 47.5 30-gallon ester gum varnish 47. York whiting 3.0 Zinc-aluminum hydroxide paste 2.0

In this case, the chlorination of the Chinawood oil is continued until six atoms of chlorine have been attached to three double bond unsaturations of the nine existing double bond unsaturations found in the glyceride structure.

After the oil has been chlorinated as described, 47.5 parts of the 30 gallon ester gum varnish are then added to the hexa-chlorinated oil. The ester gum resin varnish is prepared, as follows:

Raw China-wood oil and the ester gum are heated to a temperature of about 450 F. until the desired body is obtained. The varnish may be cut to any desired viscosity through the addition of raw or heat bodied China-Wood oil.

Water 800 Concentrated ammonium hydroxide x72 The procedure in preparing the paste is substantially the same as in the preparation of the paste described in the preceding example.

The mixing of the chlorinated oil, zinc-aluminum paste and pigments, followed by the printing is also substantially the same as that described in the preceding example.

In the above specification, I have given examples and suggested certain modifications for the purpose of illustrating the invention, and without in any way attempting to exhaustively cover the various modifications and application of my invention. Similarly, I have expressed certain theories which I have developed in the course of my investigations with this invention which, I believe, may be helpful to those who subsequently apply my invention in practice. However, these theoriesare not to be construed as absolutely corroot, and since my inventionis in no way dependent upon the correctness of any theory which I have expressed, it is to be understood that the scope of my invention and claims is in no way limited thereby.

I claim:

1. The method ofpreparing a fast-drying coating composition which comprises preparing a vehicle including an oil, chosen from the group consisting of drying and semi-drying oils, which has been chlorinated, and an activating paste including a reactive metallic substance chosen from the group consisting of the oxides and hydroxides of zinc, iron, mercury, antimony, copper, tin cobait, nickel, chromium and magnesium, said metallic substance being wetted by water, finally mixing the chlorinated oil and the activating paste.

2. The method of preparing a fast-drying printing ink which comprises preparing a vehicle including an oil, chosen from the group consisting of drying and semi-drying oils, which has been chlorinated, and an activating paste including a reactive metallic substance chosen from the group consisting of the oxides and hydroxides of zinc, iron, mercury, antimony, copper tin, cobalt, nickel, chromium and magnesium, said metallic substance being wetted by water, finally mixing the chlorinated oil and the activating paste with pigments.

3. The method of preparing a fast-drying vehicle which comprises preparing a mixture including a chlorinated oil chosen from the group consisting of drying and semi-drying oils and a resin varnish, then preparing an activating paste including a reactive metallic substance chosen from the group consisting of the oxides and hydroxides of zinc, iron, mercury, antimony, copper, tin, cobalt, nickel, chromium and magnesium, finally mixing the chlorinated oil mixture and the activating paste until a homogeneous vehicle is obtained.

4. The method oi preparing a fast-drying printing ink which comprises the steps of pass ing chlorine through an oil, chosen from the group of drying and semi-drying oils, until the desired chlorination is obtained, then preparing an activating paste including a reactive metallic substance chosen from the group consisting of the oxides and hydroxides of zinc, iron, mercury,

antimony, copper, tin, cobalt, nickel, chromium and magnesium, finally mixing the chlorinated oil and the activating paste with pigments until a homogeneous ink product is obtained.

5. The method of preparing a fast-drying printing ink as described in claim 4, in which a resin varnish is added to the chlorinated oil.

6. The method of preparing a fast-drying printing ink which comprises the steps of passing chlorine through an oxidized oil, chosen from the group consisting of drying and semi-drying oils, until the desired chlorination is obtained, then preparing an activating paste including a reactive metallic substance and water, said metallic substance being chosen irom the group consisting of the oxides and hydroxides of zinc, iron. mercury, antimony, copper, tin, cobalt, nickel, chromium and magnesium, mixing the chlorinated oil and the activating paste to form a vehicle, finally adding pigments of any desired color to the vehicle and mixing until a homogeneous ink product is obtained.

7. The method or preparing a fast-drying printing ink as described in claim 6, in which a resin varnish is added to the vehicle.

. 8. A fast-drying coating composition which comprises a chlorinated oil, chosen from the group consisting of drying and semi-drying oils, and a reactive metallic substance in the form of a water paste, said reactive metallic substance being chosen from a group consisting of the oxides and hydroxides of zinc, iron, mercury, antimony, copper, tin, cobalt, nickel, chromium and magnesium, said chlorinated oil and the reactive metallic substance adapted to react to dry the composition.

9. A fast-drying coating composition as described in claim 8, in which a resin varnish is added to the chlorinated oil.

10. A fast-drying printing ink composition which comprises a mixture of pigments, chlorinated oil chosen from the group consisting of drying and semi-drying oils, and a water paste including a reactive metallic substance, said reactive metallic substance being chosen from a group consisting of the oxides and hydroxides of zinc, iron, mercury, antimony, copper, tin, cobalt, nickel, chromium and magnesium, said chlorinated oil and reactive metallic substance adapted to react to dry the ink composition.

11. A fast-drying printing ink as described in claim 10, in which a resin varnish is added to the chlorinated oil.

WALTER J. KOENIG. 

